Niobium(V) oxide coated on thin glass-ceramic rod as a solid phase microextraction fiber

The efficiency of niobium(V) oxide as a sorbent phase for solid phase microextraction (SPME) was investigated. The thin glass-ceramic rod was coated with niobium(V) oxide using chemical vapor deposition and Nb₂O₅ as a chemical precursor. Optimum conditions for the preparation and conditioning of the fibers are presented. The fibers were used for the extraction of a mixture of alcohols and a mixture of phenols from the headspace samples. The results obtained proved the suitability of niobium(V) oxide as a new SPME fiber. The calibration graphs for alcohols and phenols in a concentration range of 50-1000 μg l⁻¹ were linear (r > 0.995) and the detection limits were below 0.8 μg l⁻¹ level. The repeatability for one fiber (n = 6) under similar conditions was between 3 and 10.4%. The fiber-to-fiber reproducibility (n = 6) was between 5 and 15%.     

Analysis of sesquiterpene emissions by plants using solid phase microextraction

Solid phase microextraction (SPME) was characterized for the sampling and analysis of sesquiterpenes (SQTs) emitted by plants. Constant mixing ratio SQT standards were produced using a capillary diffusion system. Polydimethylsiloxane SPME fibers were characterized with respect to relative absorption of SQTs, and the effects of sample linear velocity and sample relative humidity on SQT absorption. SPME was then utilized to measure SQT emissions from gray pine (Pinus sabiniana) and ponderosa pine (Pinus ponderosa). Total SQT emission rates at a photosynthetic photon flux density of 1200 μmol m⁻² s⁻¹ and 28 °C ranged 0.025–0.050 μgC m⁻² h⁻¹ (α-farnesene) and 0.450–3.325 μgC m⁻² h⁻¹ (α-farnesene, β-farnesene, and α-bergamotene) for gray pine and ponderosa pine, respectively.     

Semi-automated in vivo solid-phase microextraction sampling and the diffusion-based interface calibration model to determine the pharmacokinetics of methoxyfenoterol and fenoterol in rats

In vivo solid-phase microextraction (SPME) can be used to sample the circulating blood of animals without the need to withdraw a representative blood sample. In this study, in vivo SPME in combination with liquid–chromatography tandem mass spectrometry (LC–MS/MS) was used to determine the pharmacokinetics of two drug analytes, R,R-fenoterol and R,R-methoxyfenoterol, administered as 5 mg kg⁻¹i.v. bolus doses to groups of 5 rats. This research illustrates, for the first time, the feasibility of the diffusion-based calibration interface model for in vivo SPME studies. To provide a constant sampling rate as required for the diffusion-based interface model, partial automation of the SPME sampling of the analytes from the circulating blood was accomplished using an automated blood sampling system. The use of the blood sampling system allowed automation of all SPME sampling steps in vivo, except for the insertion and removal of the SPME probe from the sampling interface. The results from in vivo SPME were compared to the conventional method based on blood withdrawal and sample clean up by plasma protein precipitation. Both whole blood and plasma concentrations were determined by the conventional method. The concentrations of methoxyfenoterol and fenoterol obtained by SPME generally concur with the whole blood concentrations determined by the conventional method indicating the utility of the proposed method. The proposed diffusion-based interface model has several advantages over other kinetic calibration models for in vivo SPME sampling including (i) it does not require the addition of a standard into the sample matrix during in vivo studies, (ii) it is simple and rapid and eliminates the need to pre-load appropriate standard onto the SPME extraction phase and (iii) the calibration constant for SPME can be calculated based on the diffusion coefficient, extraction time, fiber length and radius, and size of the boundary layer. In the current study, the experimental calibration constants of 338.9 ± 30 mm⁻³ and 298.5 ± 25 mm⁻³ are in excellent agreement with the theoretical calibration constants of 307.9 mm⁻³ and 316.0 mm⁻³ for fenoterol and methoxyfenoterol respectively.     

Dynamic non-equilibrium SPME combined with GC, PICI, and ion trap MS for determination of organophosphate esters in air

Methodology for time-weighted average (TWA) air measurements of semivolatile organophosphate triesters, widely used flame-retardants and plasticizers, and common indoor pollutants is presented. Dynamic non-equilibrium solid-phase microextraction (SPME) for air sampling, in combination with GC/PICI and ion trap tandem MS, yields a fast, almost solvent-free method with low detection limits. Methanol was used as reagent gas for PICI, yielding stable protonated molecules and few fragments. A field sampler, in which a pumped airflow over three polydimethylsiloxane (PDMS) 100-μm fibers in series was applied, was constructed, evaluated, and used for the measurements. The method LODs were in the range 2–26 ng m⁻³ for a sampling period of 2 h. The uptake on the SPME fibers was shown to be about five times faster for triphenyl phosphate compared to the other investigated organophosphate esters, most likely due to more lipophilic properties of the aromatic compound. The boundary layer for triphenyl phosphate when using a 100-μm PDMS sorbent was determined to 0.08 mm at a linear air velocity of 34 cm s⁻¹. Five different organophosphate triesters were detected in air from a laboratory and a lecture hall, at concentrations ranging from 7 ng m⁻³ up to 2.8 μg m⁻³.     

Coupled in-tube and on-fibre solid-phase microextractions for cleanup and preconcentration of organic micropollutants from aqueous samples and analysis by gas chromatography-mass spectrometry

Matrix interference removal is an important step when large volumes of aqueous samples are required to be processed to detect trace levels of analytes. A combination of two sample extraction methods has been used in this work with the aim of cleanup and preconcentration of analytes. For first objective, mild but preferential sorption of a range of analytes has been performed with in-tube solid-phase microextraction (SPME) using polytetrafluoroethylene (PTFE) tubing, and for the second, the eluate from in-tube SPME was subjected to on-fibre SPME using DVB/Caboxen/PDMS (30/50 μm) fibre. Knitting of PTFE tubing created secondary flow pattern that enhanced radial diffusion and retention of organic analytes. Up to 2 mg L⁻¹ of a broad range of substances that are not extracted by PTFE include nitrogen containing aromatic heterocyclic compounds, anilines, phenols and certain organophosphorus pesticides, thus providing a clean extract using this method of sample preparation. The proposed combination of in-tube and on-fibre SPME produced a rectilinear calibration graph over 0.03-150 μg L⁻¹ of a range of analytes using 60 mL of aqueous sample. The overall recovery of analytes was in the range 27-78%. The detection limits were between 6.1 and 21.8 ng L⁻¹. The R.S.D. was in range 5.4-8.2% and 4.2-6.5% in the analysis of respectively 2 and 20 μg L⁻¹ of analytes.     

Burning velocity measurement of HFC-41, HFC-152, and HFC-161 by the spherical-vessel method

The burning velocities of fluoromethane (HFC-41), 1,2-difluoroethane (HFC-152), fluoroethane (HFC-161) and ethane were measured by the spherical-vessel (SV) method at room temperature and at initial pressures of 80-107 kPa over a wide range of HFC/air equivalence ratios (?). The burning velocities were determined from the measured pressure increases by application of a spherical flame model. Schlieren photography was used to directly observe flame propagation behavior in a cylindrical vessel equipped with optical windows. The time evolution of the flame radii derived from the pressure increases agreed with the time evolution observed with the Schlieren technique. The maximum burning velocities of HFC-41, HFC-152, HFC-161 and ethane were 28.3 cm s⁻¹ at ? = 1.01, 30.1 cm s⁻¹ at ? = 1.07, 38.3 cm s⁻¹ at ? = 1.07 and 40.9 cm s⁻¹ at ? = 1.05, respectively. The maximum burning velocities for the HFCs, including previously reported C₁ and C₂ fluoroalkanes, decreased with increasing F-substitution rate (the ratio of the number of F atoms to the sum of the number of H and F atoms). The concentrations of chemical species in the flames were investigated by means of an equilibrium calculation, and the results suggested that the burning velocity was correlated with the concentrations of H and OH radicals that were not deactivated by F radicals in the flame. The results also suggested that the burning velocities were linearly related to the heats of combustion of the C₁ and C₂ fluoroalkanes.     

In situ fabrication of nanostructured titania coating on the surface of titanium wire: A new approach for preparation of solid-phase microextraction fiber

Nanostructured titania-based solid-phase microextraction (SPME) fibers were fabricated through the in situ oxidation of titanium wires with H₂O₂ (30%, w/w) at 80 °C for 24 h. The obtained SPME fibers possess a ∼1.2 μm thick nanostructured coating consisting of ∼100 nm titania walls and 100-200 nm pores. The use of these fibers for headspace SPME coupled with gas chromatography with electron capture detection (GC-ECD) resulted in improved analysis of dichlorodiphenyltrichloroethane (DDT) and its degradation products. The presented method to detect DDT and its degradation products has high sensitivity (0.20-0.98 ng L⁻¹), high precision (relative standard deviation R.S.D. = 9.4-16%, n = 5), a wide linear range (5-5000 ng L⁻¹), and good linearity (coefficient of estimation R² = 0.991-0.998). As the nanostructured titania was in situ formed on the surface of a titanium wire, the coating was uniformly and strongly adhered on the titanium wire. Because of the inherent chemical stability of the titania coating and the mechanical durability of the titanium wire substrate, this new SPME fiber exhibited long life span (over 150 times).     

Development of polymethylphenylsiloxane-coated fiber for solid-phase microextraction and its analytical application of qualitative and semi-quantitative of organochlorine and pyrethroid pesticides in vegetables

An approach to the synthesis of hydroxyl-terminated polymethylphenylsiloxane (PMPS-OH) was proposed and the synthesized PMPS-OH was successfully applied as a precursor to prepare a novel coating for solid-phase microextraction (SPME) via the sol-gel process. The thickness and length of the prepared coating was 70 μm and 1.5 cm, respectively. The extraction efficiency of the PMPS-coated fiber for selected pesticides was higher than that of commercial fibers including 100 μm polydimethylsiloxane (PDMS), 85 μm polyacrylate (PA) and 65 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB). The influence of the extraction process, extraction temperature, extraction time, stirring rate, ionic strength, GC inlet conditions, desorption temperature and time for PMPS-coated fiber application was studied and optimized. Several experiments were carried out to evaluate the analytical characteristics of the proposed SPME-GC-ECD method under optimized conditions. The linearity was from 0.5 to 100 ng g⁻¹ for p,p′-DDE, p,p′-DDD and bifenthrin, and from 2 to 100 ng g⁻¹ for o,p′-DDT, p,p′-DDT, fenpropathrin, beta-cyfluthrin and cyhalothrin. The detection limits of these pesticides were between 0.13 and 1.45 ng g⁻¹. The recovery of the pesticides spiked in various vegetables at 4 ng g⁻¹ ranged from 42.9% to 105.3%, and the relative standard deviations were less than 16.2%.     

Application of solid-phase microextraction for the determination of organophosphorus pesticides in textiles by gas chromatography with mass spectrometry

A method based on solid-phase microextraction (SPME) and gas chromatography with mass spectrometry (GC/MS) for the determination of 18 organophosphorus pesticides (OPPs) in textiles is described. Commercially available SPME fibers, 100 μm PDMS and 85 μm PA, were compared and 85 μm PA exhibited better performance to the OPPs. Various parameters affecting SPME, including extraction and desorption time, extraction temperature, salinity and pH, were studied. The optimized conditions were: 35 min extraction at 25 °C, 5% NaSO₄ content, pH 7.0, and 3.5 min desorption in GC injector port at 250 °C. The linear ranges of the SPME-GC/MS method were 0.1-500 μg L⁻¹ for most of the OPPs. The limits of detection (LODs) ranged from 0.01 μg L⁻¹ (for bromophos-ethyl) to 55 μg L⁻¹ (for azinphos-methyl) and the RSDs were between 0.66% and 9.22%. The optimized method was then used to analyze 18 OPPs in textile sample, and the determined recoveries were ranged from 76.7% to 126.8%. Moreover, the distribution coefficients of the OPPs between 85 μm PA fiber and simulative sweat solution (K_pa/s) were determined. The determined K_pa/s of the OPPs correlated well with their octanol-water partition coefficients (r = 0.764 and 0.678) and water solubility (r = −0.892 and −0.863).     

Determination of ethoprop, diazinon, disulfoton and fenthion using dynamic hollow fiber-protected liquid-phase microextraction coupled with gas chromatography-mass spectrometry

A technique for the analysis of organophosphorus pesticides (ethoprop, diazinon, disulfoton, fenthion) in aqueous sample using liquid-phase microextraction (LPME), coupled with gas chromatography-mass spectrometry (GC-MS) was developed. A small section of a hollow fiber inserted into the needle of GC syringe and filled with the 3.5 μl of organic solvent was used to extract pesticides from a 20 ml aqueous sample. The limits of detection (LOD) with the selected ion monitoring (SIM) mode varied from 0.2 to 0.006 μg/l. The calibration curves were linear over three orders of magnitude with R² ≥ 0.996. The relative standard deviations of the analysis (inter- and intra-day) were 5-8%, and the relative recoveries from the lake water sample were greater than 83%. The results were compared with results obtained using solid-phase microextraction (SPME/GC/MS).     

Pesticide analysis in herbal infusions by solid-phase microextraction and gas chromatography with atomic emission detection

A direct immersion solid-phase microextraction (SPME) procedure was used in combination with capillary gas chromatography with atomic emission detection (GC-AED) for the determination of 10 pesticides (organochlorines, organophosphorus compounds and pyrethrins) in herbal and tea infusions. Ionic strength, sample dilution and time and temperature of the absorption and desorption stages were some of the parameters investigated in order to select the optimum conditions for SPME with a 100 μm PDMS fiber-coating. Element-specific detection and quantification was carried out by monitoring the chlorine (479 nm) and bromine (478 nm) emission lines, which provided nearly specific chromatograms. Calibration was carried out by using a spiked sample infusion. The detection limits varied between 11.9 ng ml⁻¹ for deltamethrin and 0.03 ng ml⁻¹ for p,p′-DDE and p,p′-DDD. The recoveries ranged from 73.5% for deltamethrin to 108.3% for p,p′-DDT in a spiked white tea infusion. Two of the eight samples analyzed contained low levels of some the pesticides considered.     

Quantification of benzene,toluene, ethylbenzene and o-xylene in internal combustion engine exhaust with time-weighted average solid phase microextraction and gas chromatography mass spectrometry

A new and simple method for benzene, toluene, ethylbenzene and o-xylene (BTEX) quantification in vehicle exhaust was developed based on diffusion-controlled extraction onto a retracted solid-phase microextraction (SPME) fiber coating. The rationale was to develop a method based on existing and proven SPME technology that is feasible for field adaptation in developing countries. Passive sampling with SPME fiber retracted into the needle extracted nearly two orders of magnitude less mass (n) compared with exposed fiber (outside of needle) and sampling was in a time weighted-averaging (TWA) mode. Both the sampling time (t) and fiber retraction depth (Z) were adjusted to quantify a wider range of C_gas. Extraction and quantification is conducted in a non-equilibrium mode. Effects of C_gas, t, Z and T were tested. In addition, contribution of n extracted by metallic surfaces of needle assembly without SPME coating was studied. Effects of sample storage time on n loss was studied. Retracted TWA–SPME extractions followed the theoretical model. Extracted n of BTEX was proportional to C_gas, t, D_g, T and inversely proportional to Z. Method detection limits were 1.8, 2.7, 2.1 and 5.2 mg m⁻³ (0.51, 0.83, 0.66 and 1.62 ppm) for BTEX, respectively. The contribution of extraction onto metallic surfaces was reproducible and influenced by C_gas and t and less so by T and by the Z. The new method was applied to measure BTEX in the exhaust gas of a Ford Crown Victoria 1995 and compared with a whole gas and direct injection method.     

Preparation and evaluation of solid-phase microextraction fibres based on functionalized latex nanoparticle coatings for trace analysis of inorganic anions

The use of a functionalized latex nanoparticle coating as a new sorbent phase for solid-phase microextraction (SPME) was examined. By means of electrostatic absorption onto ionized silanol groups, a fused-silica rod was coated with polymeric nanoparticles functionalized with quaternary ammonium groups. Optimum conditions for the preparation of the coated fibre are presented. The fibre was used for the extraction of a mixture of seven anions from water samples which are analysed by coupling the SPME fibre to an ion chromatographic system via a special interface. The results obtained proved the suitability of this novel coating as a new SPME fibre. A linear calibration for the target analytes was achieved over the concentration range from 5 μg L⁻¹ to 5 mg L⁻¹ (r² > 0.988), while limits of detection for these ions were all below 3.7 μg L⁻¹ (S/N = 3). The reproducibility of a single fibre (n = 4) under similar conditions was between 7 and 12%, while the fibre to fibre reproducibility (n = 5) was between 8.9 and 14%.     

Mesoporous TiO2 nanoparticles for highly sensitive solid-phase microextraction of organochlorine pesticides

Mesoporous TiO₂ nanoparticles were synthesized with the hydrothermal method and characterized by powder X-ray diffraction (PXRD) and transmission electron microscope (TEM). Then a superior solid-phase microextraction (SPME) fiber was fabricated by sequentially coating the stainless steel fiber with silicone sealant film and mesoporous TiO₂ powder. The developed fiber possessed a homogeneous surface and a long life-span up to 100 times at direct immersing (DI) extraction mode. Under the optimized conditions, the extraction efficiencies of the self-made 17 μm TiO₂ fiber for six organochlorine pesticides (OCPs) were higher than those of the two commercial fibers (65 μm PDMS/DVB and 85 μm PA fibers) which were much thicker than the former. As for analytical performance, low detection limits (0.08–0.60 ng L⁻¹) and wide linearity (5–5000 ng L⁻¹) were achieved under the optimal conditions. The repeatabilities (n = 5) for single fiber were between 2.8 and 12.3%, while the reproducibilities (n = 3) of fiber-to-fiber were in the range of 3.7–15.7%. The proposed fiber was successfully applied to the sensitive analysis of OCPs in real water samples and four of the six analytes were detected from the rainwater and the lake water samples.     

Dynamic solid phase microextraction sampling for reactive terpenes in the presence of ozone

Dynamic gas sampling using solid phase microextraction (SPME) was evaluated for recovery of reactive terpenes and terpenoids in the presence of ozone. For limonene, α-terpineol and dihydromyrcenol in the 20-60 ppb range, this method achieves >80% recovery for ozone mixing ratios up to 100 ppb. Both the experimental results and a model analysis indicate that higher ozone concentrations and longer sampling times result in lower percent recovery. Typically greater than 90% recovery and ppb level method detection limits were achieved with a 5 min sample time. Increasing the flow rate from 100 to 400 sccm flow (5-20 cm s⁻¹) through the active sampler did not significantly affect sensitivity or recovery in most cases, probably due to negligible mass-transfer improvements. The recovery for each compound improves when sampling from a mixture of different species than that from a single compound sample. This may be due to competition for ozone amongst adsorbed species. Dynamic SPME sampling can improve detection and quantification of terpenes in reactive environments, especially for low vapor pressure (<5 mm Hg at 25 °C) compounds that can be adsorbed to ozone scrubbers used in other methods.     

Preparation by low-temperature nonthermal plasma of graphite fiber and its characteristics for solid-phase microextraction

Low-temperature nonthermal plasma has been used to prepare solid-phase microextraction (SPME) fibers with high adsorbability, long-term serviceability, and high reproducibility. Graphite rods serving as fiber precursors were treated by an air plasma discharged at 15.2-15.5 kV for a duration of 8 min. Sampling results revealed that the adsorptive capacity of the homemade fiber was 2.5-34.6 times that of a polyacrylate (PA) fiber for alcohols (methanol, ethanol, isopropyl alcohol, n-butyl alcohol), and about 1.4-1.6 times and 2.5-5.1 times that of an activated carbon fiber (ACF) for alcohols and BTEX (benzene, toluene, ethylbenzene, and xylenes), respectively. It is confirmed from FTIR (Fourier transform infrared spectrophotometer) and SEM (scanning electron microscope) analyses that the improvement in the adsorptive performance attributed to increased surface energy and roughness of the graphite fiber. Using gas chromatography (GC)-flame-ionization detector (FID), the limits of detection (LODs) of the alcohols and BTEX ranged between 0.19 and 3.75 μg L⁻¹, the linear ranges were between 0.6 and 35619 μg L⁻¹ with good linearity (R² = 0.9964-0.9997). It was demonstrated that nonthermal plasma offers a fast and simple method for preparing an efficient graphite SPME fiber, and that SPME using the homemade fiber represents a sensitive and selective extraction method for the analysis of a wide range of organic compounds.     

Preparation and evaluation of mesoporous cellular foams coating of solid-phase microextraction fibers by determination of tetrabromobisphenol A,tetrabromobisphenol S and related compounds

Two kinds of mesoporous cellular foams (MCFs), including mesoporous silica materials (MCF-1) and phenyl modified mesoporous materials (Ph-MCF-1), were synthesized and for the first time used as fiber-coating materials for solid-phase microextraction (SPME). By using stainless steel wire as the supporting core, four types of fibers were prepared by sol–gel method and immobilized by epoxy-resin method. To evaluate the performance of the home-made fibers for SPME, seven brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA), tetrabromobisphenol S (TBBPS) and related compounds were selected as analytes. The main parameters that affect the extraction and desorption efficiencies, such as extraction temperature, extraction time, desorption time, stirring rate and ionic strength of samples were investigated and optimized. The optimized SPME coupled with high performance liquid chromatography (HPLC) was successfully applied to the determination of the seven BFRs in water samples. The linearity range was from 5.0 to 1000 μg L⁻¹ for each compound except TBBPS (from 1.0 to 1000 μg L⁻¹), with the correlation coefficients (r²) ranging from 0.9993 to 0.9999. The limits of detection of the method were 0.4–0.9 μg L⁻¹. The relative standard deviations varied from 1.2 to 5.1% (n = 5). The repeatability of fiber-to-fiber and batch-to-batch was 2.5–6.5% and 3.2–6.7%. The recoveries of the BFRs from aqueous samples were in the range between 86.5 and 103.6%. Compared with three commercial fibers (100 μm PDMS, 85 μm PA and 65 μm PDMS/DVB), the MCFs-coated fiber showed about 3.5-fold higher extraction efficiency.     

Preparation of C18 composite solid-phase microextraction fiber and its application to the determination of organochlorine pesticides in water samples

In this work, a C18 composite solid-phase microextraction (SPME) fiber was prepared with a new method and applied to the analysis of organochlorine pesticides (OCPs) in water sample. A stainless steel wire (o.d. 127 μm) was used as the substrate, and a mixture of the C18 particle (3.5 μm) and the 184 silicone was used as the coating material. During the process of fiber preparation, a section of capillary column was used to fix the mixture onto the stainless steel wire and to ensure the constant of coating thickness. The prepared fiber showed excellent thermal stability and solvent resistance. By coupling with gas chromatography–mass spectrometry (GC–MS), the fiber exhibited wide linearity (2–500 ng L⁻¹) and good sensitivity for the determination of six OCPs in water samples, the OCPs tested included hexachlorobezene, trans-chlordane, cis-chlordane, o,p-DDT, p,p-DDT and mirex. Not only the extraction performance of the newly prepared fiber was more than seven times higher than those of commercial fibers, the limits of detections (LODs) (0.059–0.151 ng L⁻¹) for OCPs achieved under optimized conditions were also lower than those of reported SPME methods. The fiber was successfully applied to the determination of OCPs in real water samples by using developed SPME–GC–MS method.     

Silicone glue coated stainless steel wire for solid phase microextraction

A new solid phase microextraction (SPME) fiber based on high-temperature silicone glue coated on a stainless steel wire is presented. The fiber coating can be prepared easily in a few minutes, it is mechanically stable and exhibits relatively high thermal stability (up to 260 °C). The extraction properties of the fiber to benzene, toluene, ethylbenzene, and xylenes (BTEX) were examined using both direct and headspace SPME modes coupled to gas chromatography-flame ionization detection. The effects of the extraction and desorption parameters including extraction and desorption time, sampling and desorption temperature, and ionic strength on the extraction/desorption efficiency have been studied. For both headspace and direct SPME the calibration graphs were linear in the concentration range from 0.5 μg L⁻¹ to 10 mg L⁻¹ (R² > 0.996) and detection limits ranged from 0.07 to 0.24 μg L⁻¹. Single fiber repeatability and fiber-to-fiber reproducibility were less than 6.8 and 21.5%, respectively. Finally, headspace SPME was applied to determine BTEX in petrol station waste waters with spiked recoveries in the range of 89.7-105.2%.     

Determination of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in human urine by HS-SPME gas chromatography/mass spectrometry

Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L⁻¹, within- and between-run precision, as coefficient of variation, <22 and <16%, accuracy within 20% the theoretical level, and limit of detection of 6 ng L⁻¹ for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L⁻¹), ETBE (<6 ng L⁻¹), and TAME (<6 ng L⁻¹) were obtained.